Aldehyde-containing vinylaryl ethers

ABSTRACT

Disclosed herein are monomeric compounds having the formula (I): ##STR1## wherein: R, R 1 , R 2  and R 3  are independently hydrogen or alkyl having from 1 to 4 carbon atoms; 
     R 4  is arylene having 6 to 18 carbon atoms; 
     m is an integer from 1 to 4; and 
     n is an integer from 0 to 4. 
     These monomers can be homopolymerized or copolymerized with one or more other polymerizable monomers, and can particularly be copolymerized with those monomers having substituents which are susceptible to attack or degradation by a base. The resulting crosslinkable polymers are useful in relief image materials, such as photoresists and lithographic plates.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to organic materials which are particularlyuseful in preparing polymers which are useful in the graphic arts. Inone of its aspects, this invention relates to the use of such materialsto prepare crosslinkable polymers which can be incorporated intoradiation-sensitive elements to obtain a desirable combination ofproperties.

2. Description of the Prior Art

Conventional vinyldiaryl ether monomers and polymers formed therefromare disclosed in U.S. Pat. No. 2,522,501, issued Sept. 19, 1950. Themonomers are generally prepared by reacting a diaryl ether with acetylchloride, forming a carbinol by reduction and dehydrating the resultingcarbinol. Polymerization occurs when the monomers are heated in air athigh temperatures. The disclosed monomers and the polymers preparedtherefrom contain only unsubstituted aryl groups.

U.S. Pat. No. 3,055,947, issued Sept. 25, 1962, discloses vinylarylether monomers which are formed from the reaction (at 50° to 200° C.) ofa haloalkyl aromatic halomethyl compound ##STR2## with an hydroxyl R₁ OHin the presence of a base metal catalyst, wherein:

Ar is aryl;

R is hydrogen or methyl;

R₁ is hydrogen, alkyl, aryl or aralkyl;

X is a halide;

Z and Z₁ are either hydrogen or halide; and

n is an integer of 1 to 3.

R₁ can also be a substituted aryl radical. This reference is typical ofthe art which shows the preparation of vinylaryl ether monomers by areaction of a halogenated alkylbenzene with a phenol in a basicenvironment. One of ordinary skill in the art would not expect thedisclosed method to be useful in the preparation of aldehyde-containingpolymers because it is expected that the aldehyde would react withanother aldehyde group or with the vinyl moiety thereby causingcrosslinking.

It is desirable, however, to form vinylaryl ether monomers which havealdehyde substituents. Polymers formed from such monomers would providecrosslinking sites for further reaction with various reagents, such asamines and the like. In the reaction environment taught by U.S. Pat. No.3,055,947, it is expected that any aldehyde-containing monomers wouldprematurely gel because of spontaneous crosslinking or polymerization.Furthermore, Ringsdorf et al, Macromolecular Chem., 31, pages 27 through49 (1959), disclose that vinyl compounds containing aldehyde groupspolymerize to form insoluble polymers. One would expect a monomercontaining an aldehyde group to form a crosslinked polymer during anyconventional polymerization reaction.

Gibson et al, J. Poly. Sci:Poly. Chem. Ed., 12, pages 2141 through 2143(1974) and Gibson, Macromolecules, 8, pages 89 and 90 (1975), disclosethat homopolymers and copolymers containing recurring units ofvinylbenzyl phenylethers can be prepared by reaction of a phenol with apolymer containing recurring units of vinylbenzyl chloride in a basicenvironment. The phenyl groups can be substituted with a variety ofradicals, including aldehydes. Not all copolymers containingaldehyde-substituted aryl ether units can be made by this method,however. In the basic environment of the phenol-poly(vinyl benzylchloride) reaction, many copolymers containing certain substituents orfunctional groups hydrolyze or degrade. These substituents are reactivewith and susceptible to attack or degradation by a base. By "susceptibleto attack or degradation by a base" is meant an ability to undergo achemical reaction with a base to form a species with a chemicalstructure different from that of the starting species. This abilityincludes such severe alterations that the degraded material cannot berestored simply by neutralizing the product species with an acid.Examples of such substituents and monomers containing them are givenbelow in the Detailed Description of the Present Invention. Therefore,one could not make aldehyde-containing copolymers by the methoddescribed in the Gibson references.

Hence, a method of producing polymerizable vinylaryl ether monomerscontaining aldehyde groups, whereby gelation due to spontaneouspolymerization and/or crosslinking is not allowed to occur, would behighly desirable. It would be further desirable to have a method ofproducing uncrosslinked polymers from such vinylaryl ether monomers.Such polymers could also contain recurring units of polymerizablemonomers having functional groups which may be susceptible to attack ordegradation by a base.

SUMMARY OF THE INVENTION

The present invention provides aldehyde-containing vinylaryl ethermonomers which are easily prepared from readily available startingmaterials. Further, the present invention provides organicsolvent-soluble polymers formed from the aldehyde-containing monomers.These polymers can comprise recurring units of monomers havingsubstituents which are susceptible to attack or degradation by a base.The method of the present invention of preparing these polymers alsoavoids gelation.

The polymers of the present invention are useful in many applications,but are particularly useful with radiation-sensitive materials used inthe graphic arts. These polymers with pendant aldehyde groups can becrosslinked with reagents such as amines to provide organicsolvent-insoluble areas, such as in light exposed regions of alithographic plate or a photoresist, thereby providing relief negativeimages.

An especially preferred use of these copolymers is for crosslinking withdiamino compounds as described in copending U.S. Patent Application Ser.No. 872,852, filed Jan. 27, 1978 by Adin and Wilson and entitled"Photocrosslinkable Carbonyl-Containing Polymeric Composition andElements".

One aspect of the present invention comprises a compound having theformula (I): ##STR3## wherein: R, R¹, R² and R³ are independentlyhydrogen or alkyl having from 1 to 4 carbon atoms;

R⁴ is arylene having 6 to 18 carbon atoms;

m is an integer from 1 to 4; and

n is an integer from 0 to 4.

In another aspect of the present invention, a method of making acompound having formula (I) comprises reacting, in the presence of anacid acceptor, a compound having the formula: ##STR4## with a compoundhaving the formula HO-R⁴ --CHR³)_(n) CHO, wherein:

X is a halide; and

R, R¹, R², R³, R⁴, m and n are as defined above.

Still another aspect of the present invention comprises an uncrosslinkedpolymer formed from:

(a) about 1 to 99 mole percent of one or more monomers having formula(I); and

(b) from 1 to about 99 mole percent of one or more additionalethylenically unsaturated polymerizable monomers having substituentswhich are susceptible to degradation by a base.

In still another aspect of the present invention, a method of making anuncrosslinked polymer formed from:

(a) about 1 to 100 mole percent of one or more monomers having formula(I); and

(b) from about 0 to about 99 mole percent of one or more additionalethylenically unsaturated polymerizable monomers, comprises:

(1) reacting, in the presence of an acid acceptor, a compound having theformula: ##STR5## with a compound having the formula HO-R⁴ --CHR³)_(n)CHO, wherein X is halide, and R, R¹, R², R³, R⁴, m and n are as definedabove for formula (I); and

(2) polymerizing the resulting aldehyde-containing monomer orcopolymerizing the monomer with the one or more additional ethylenicallyunsaturated polymerizable monomers.

DETAILED DESCRIPTION OF THE INVENTION

In formula (I) describing the monomers of the present invention, R, R¹,R² and R³ are independently hydrogen or alkyl having from 1 to 4 carbonatoms, such as methyl, ethyl, propyl, butyl, isopropyl, tert-butyl andthe like. R⁴ is arylene having from 6 to 18 carbon atoms, such asphenylene, naphthylene, anthrylene, biphenylylene, including substitutedarylenes such as arylenes substituted with halides or lower alkyls asdescribed for R, and those containing other substituents, such as nitro,alkoxy, and the like.

Exemplary monomers corresponding to formula (I) include o-, p- orm-formylphenyl vinylbenzyl ether, o-, p- or m-(2-formylethoxy)phenylvinylbenzyl ether, 2-, 3- or 4-formylnaphthyl vinylbenzyl ether, (3- or4-formyl-2-methylphenyl) vinylbenzyl ether, formylbiphenylyl vinylbenzylethers, and the like.

Monomers of the present invention which are preferred are those havingformula (I) wherein R, R¹, R², and R³ are all hydrogen, and mostpreferably when, additionally, m is 1 and n is 0. Preferred monomers areo-, p- and m-formylphenyl vinylbenzyl ethers.

The method of making monomers of formula (I) comprises reactingvinylaralkyl halides having the formula: ##STR6## wherein: R, R¹, R² andm are defined as in formula (I); and

X is halide, such as fluoride, chloride, bromide or iodide, with analdehyde-containing hydroxyaryl having the formula HO-R⁴ --CHR³)_(n) CHOwherein R³, R⁴ and n are defined as in formula (I).

Exemplary vinylaryl halides include o-, p- or m-vinylbenzyl chloride,o-, p- or m-vinylbenzyl bromide and the like. It is noted that manyother halides could be used to prepare the monomers of formula (I).Similarly, exemplary hydroxyaryls include substituted or unsubstitutedhydroxybenzaldehydes, salicylaldehydes, hydroxynaphthaldehydes,hydroxyanthraldehydes and the like.

The described reactants are reacted in the presence of an acid acceptorwhich is defined as a compound which neutralizes, or forms a salt with,the released halo acid. Exemplary acid acceptors include hydroxides,such as alkali metal hydroxides, alkaline earth metal hydroxides,quaternary alkyl ammonium hydroxides and the like; alkoxides, such asaluminum butoxide, calcium isopropoxide, sodium ethoxide and the like;carbonates, such as sodium carbonate, potassium carbonate, calciumcarbonate and the like; pyridine; picoline; lutidine; weak baseion-exchange resins, such as Amberlite IR4B and Amberlite IR-45(products sold commercially by Rohm and Haas Company) and the like; andothers available in the art.

The reaction can take place in the presence of small amounts ofpolymerization inhibitors, such as o-, m- or p-dinitrobenzene,acetophenone, anilines, anthracene, p-benzoquinones, and the like andothers available in the art.

Stoichiometrically, one mole of each of the reactants is required toproduce one mole of ether and one mole of HX byproduct. It may bedesired to provide an excess of one or the other of the reactants.Suitable molar ratios of the halide to the hydroxyaryl are in the rangeof from about 1:0.9 to about 1:1.5, and preferably of from about 1:0.9to about 1:1.1.

If desired, a mutual inert solvent can be employed to dissolve thereactants or to serve as a heat transfer medium. The use of inertsolvents is particularly desirable in a continuous operation. Theproducts can be removed from the solvent by any suitable means, such asfiltration, concentration and the like. The amount of solvent is notcritical and can be in the range of from about 60 to about 95 weightpercent of the reaction mixture, and preferably from about 70 to about90 weight percent. Suitable solvents include alcohols, such as methanol,ethanol, isopropanol and the like; N,N-dimethylformamide; dimethylsulfoxide and the like.

The reaction generally proceeds at reflux temperature, which istypically in the range of from about 20° to about 100° C., andpreferably from about 70° to about 90° C. The reaction pressure can befrom subatmospheric to superatmospheric pressures of about 1000 psig.Typically, the reaction is carried out at atmospheric pressure.

The reaction time is a function of reaction temperature and theparticular reactants employed. Generally, reaction times are in therange of from about 15 to about 25 hours, but shorter times can beemployed with more active reactants, and longer times for less activereactants.

Particular reaction conditions are illustrated in Examples 1 through 3below in the preparation of particular monomeric ethers of the presentinvention.

The aldehyde-containing monomeric ethers of the present invention areuseful in making the uncrosslinked polymers of the present invention.Preferably, these polymers are organic solvent soluble. These polymerscan be crosslinked and used in elements in which it is desired to haveorganic solvent removable uncrosslinked regions and organic solventresistant crosslinked regions as in negative image lithographic plates.

These polymers are formed from about 1 to about 100 mole percent of oneor more monomers having formula (I). Preferred polymers are thosecontaining units of the preferred monomeric ethers discussed earlier.

In addition, the polymers can comprise from 0 to about 99 mole percentof recurring units derived from one or more additional ethylenicallyunsaturated polymerizable monomers, each containing, for example, atleast one ##STR7## group. Exemplary monomers include vinyl esters, suchas vinyl acetate, vinyl butyrate and the like; vinyl amides, such asacrylamide, methacrylamide, N-methylacrylamide,N-isopropylmethacrylamide and the like; vinyl nitriles, such asacrylonitrile, methacrylonitrile, 3-butenenitrile and the like; vinylketones, such as methyl vinyl ketone, diacetone acrylamide and the like;vinyl halides, such as vinyl chloride, vinyl bromide, vinylidenechloride and the like; vinyl ethers, such as methyl vinyl ether, allylmethyl ether, allyl phenyl ether and the like; unsaturated acids orfunctional derivatives thereof, such as acrylic acid, methacrylic acid,methyl acrylate, butyl methacrylate, 2-dimethylaminoethyl methacrylate,2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate and the like; olefinsand diolefins, such as ethylene, propylene, butadiene, isoprene,1,1-diphenylethylene and the like; vinyl aromatics, such as styrene,α-methylstyrene, p-chlorostyrene and the like;4,4,9-trimethyl-8-oxo-7-oxa-4-azonia-9-decene1-sulfonate;N-vinylsuccinimide; N-vinylphthalimide; N-vinylpyrazolidone; and othersavailable to those skilled in the art.

In a preferred embodiment of the present invention, the novel organicsolvent soluble uncrosslinked polymers are formed from:

(a) about 1 to about 99 mole percent of one or more monomers havingformula (I); and

(b) about 1 to about 99 mole percent of one or more additionalethylenically unsaturated polymerizable monomers having substituentswhich are susceptible to degradation by a base.

In general, such monomers are those which have substituents that wouldundergo such reactions as ester interchange, ring openings,dehydrohalogenation, Hofmann elimination, ion exchange, displacement,alkylation, anhydride ring opening, salt formation, esterification andhydrolysis in a basic environment. These reactions are described indetail in general organic chemistry textbooks, including Morrison andBoyd, Organic Chemistry, 2nd Ed., Allyl and Bacon, Inc., 1966, andMarch, Advanced Organic Chemistry:Reactions, Mechanisms, and Structure,McGraw-Hill Co., 1968, hereby incorporated herein by reference.

Exemplary of polymerizable monomers having substituents which aresusceptible to degradation by a base are vinyl esters, such as vinylacetate, vinyl butyrate and the like; vinyl amides, such as acrylamide,methacrylamide, 3-acrylamidopropane-1-sulfonic acid, heterocyclicmonomers such as N-vinyl-2-pyrrolidone, 2-phenyl-1-vinylimidazole,N-vinylsuccinimide and the like; vinyl halides, such as vinyl chloride,vinyl bromide, vinylidene chloride, vinylbenzyl chloride, 3-chloropreneand the like; vinyl nitriles, such as acrylonitrile, methacrylonitrileand the like; vinyl ketones, such as methyl vinyl ketone and the like;unsaturated acids or functional derivatives thereof, such as acrylicacid, methacrylic acid, crotonic acid, acanitic acid, α-chloroacrylicacid, maleic acid, citraconic acid, fumaric acid, methyl acrylate,isobutyl methacrylate, crotonyl acrylate, 2-chloroethyl methacrylate,2-hydroxyethyl methacrylate, maleic anhydride, itaconic anhydride andthe like; and sulfonamido-containing monomers, such asN-1-butyl-N-4-methacryloylsulfanilamide, N-(p-tolylsulfonyl)-carbamicacid (maleinimido)methyl ester,N-butyl-4-methacryloyloxybenzenesulfonamide and the like. Mixtures ofthese monomers can be used, if desired.

Most preferably, the polymers of the present invention compriserecurring units derived from sulfonamidocontaining monomers.

Although the amount of monomeric ether incorporated into the polymers ofthe preferred embodiment of the present invention can vary from about 1to about 99 mole percent, preferably the amount is from about 20 toabout 90 mole percent. The preferred amount of additional ethylenicallyunsaturated polymerizable monomers is from about 10 to about 80 molepercent.

Exemplary polymers of the present invention include poly(o-, m- orp-formylphenyl vinylbenzyl ether), poly(o-, m- or p-formylphenylvinylbenzyl ether-co-methyl methacrylate), poly(o-, m- or p-formylphenylvinylbenzyl ether-co-N-1-butyl-N-4-methacryloylsulfanilamide), poly[o-,m- or p-formylphenyl vinylbenzyl ether-co-N-(p-tolylsulfonyl) carbamicacid(maleinimido)methyl ester], poly(o-, m- or p-formylphenylvinylbenzyl ether-co-methyl vinyl ketone), poly-(o-, m- orp-formylphenyl vinylbenzylether-co-N-butyl-p-methacryloyloxybenzenesulfonamide), poly(o-, m- orp-formylphenyl vinylbenzyl ether-co-N¹ -ethyl-N⁴-methacryloylsulfanilamide), poly(o-, m- or p-formylphenyl vinylbenzylether-co-p-methanesulfonamidostyrene) and poly[o-formylphenylvinylbenzylether-co-N-(2,6-dihydroxyphenyl)acrylamide-co-2-(methacryloyloxy)ethyltrimethylammoniummethosulfate].

The method of making the polymers of the present invention comprises twosteps, the first being that of making the aldehyde-containing monomericethers. The second step comprises homopolymerization of the monomericethers, copolymerization with each other, or copolymerization with theadditional ethylenically unsaturated polymerizable monomers.

Polymerization can be carried out using techniques available to thoseskilled in the polymer chemistry art, including bulk, suspension,emulsion, solution and continuous techniques. Preferably, it is carriedout in organic solvent solutions comprising solvents such as p-dioxane,N,N-dimethylformamide, tetrahydrofuran, dimethylsulfoxide and the likeand most preferably in p-dioxane.

The temperature at which the polymers of the present invention areprepared is subject to wide variation, since this temperature dependsupon such variable features as the specific initiator and monomers used,duration of heating, pressure employed and like considerations. However,the polymerization temperature generally does not exceed about 110° C.,and most often it is in the range of from about 40° to about 100° C. Thepressure employed in the polymerization, if any, is usually onlysufficient to maintain the reaction mixture in liquid form, althougheither superatmospheric or subatmospheric pressures can be used. Theconcentration of polymerizable monomer in the polymerizable mixture canbe varied widely with concentrations up to about 80 percent by weight,and preferably from about 10 to about 50 percent by weight, based on theweight of the mixture, being satisfactory. Suitable catalysts for thepolymerization reaction include, for example, from about 0.001 to about2.0 weight percent of free radical catalysts, such as2,2'-azobis(2-methylpropionitrile), hydrogen peroxide, cumenehydroperoxide and the like. In redox polymerization systems, the usualingredients can be employed. If desired, the polymer can be isolatedfrom the reaction vehicle by freezing, salting out, concentration,precipitation in a non-solvent, such as diethyl ether, or any otherprocedure suitable for this purpose.

As indicated in U.S. Pat. No. 3,142,568, issued July 28, 1964, it issometimes advantageous to include a surface active agent or compatiblemixtures of such agents in emulsion or suspension preparation of vinylor addition polymers. Suitable wetting agents include the nonionic,ionic and amphoteric types. Such wetting agents are disclosed, forexample, in U.S. Pat. Nos. 2,600,831, issued June 17, 1952; 2,271,622,issued Feb. 3, 1942; 2,271,623, issued Feb. 3, 1942; 2,275,727, issuedMar. 10, 1942; 2,787,604, issued Apr. 2, 1957; 2,816,920, issued Dec.17, 1957 and 2,739,891, issued Mar. 27, 1956.

The molecular weights of he polymers of the present invention aresubject to wide variation, but typically are within the range of fromabout 10,000 to about 1,000,000. These polymers typically have inherentviscosities within the range of from about 0.1 to about 2.0, andpreferably from about 0.2 to about 1.4, as measured (unless otherwiseindicated) in a 1:1 (weight) phenol-chlorobenzene mixture (0.25 gpolymer per 100 ml solution) at 25° C. As used herein, the term"inherent viscosity" is determined by the formula: ##EQU1## wherein:η_(inh) is the inherent viscosity;

η_(rel) is the relative viscosity of a phenol-chlorobenzene solution ofthe polymer; and

C is the concentration in grams of polymer per 100 ml of solution.

The polymers of the present invention typically have glass transitiontemperatures within the range of from about -10° to about 150° C. Thesetemperatures can be determined by differential scanning colorimetry, asdisclosed in Techniques and Methods of Polymer Evaluation, Volume 2,Marcel Dekker, Inc., N.Y., 1970.

The polymers of the present invention are soluble in a variety oforganic solvents, including acetone, tetrahydrofuran, dichloromethane,chloroform, N,N-dimethylformamide, 2-methoxyethanol, dimethyl sulfoxide,p-dioxane and the like. By solubility of the polymer, it is meant thatthe crosslinking of the polymer results in a distinct solubilitydifferential in organic solvents such that said solvents will dissolveuncrosslinked polymer but not crosslinked polymer.

This invention is further illustrated by the following examples,although it will be understood that these examples are included merelyfor purposes of illustration and are not intended to limit the scope ofthe invention.

Examples 1 through 3 illustrate the preparation of some of thepolymerizable aldehyde-containing monomers of the present invention.

EXAMPLE 1 Preparation of o-Formylphenyl Vinylbenzyl Ether

A mixture of 235 g (1.53 mol) of vinylbenzyl chloride, 183 g (1.5 mole)of salicylaldehyde, 108.0 g of 85 percent potassium hydroxide, 2.4 g ofm-dinitrobenzene and 3.5 liters of 3A (denatured) ethanol was heated atreflux for approximately 20 hours at about 80° C. The mixture wascooled, filtered and the filtrate was concentrated to an oily solid. Theresidue was treated with ether and filtered. The filtrate was thenwashed two times with 5 percent sodium hydroxide and two times withwater. The organic phase was dried over sodium sulfate, concentrated toan oil and distilled. The yield of o-formylphenyl vinylbenzyl ether was149 g (41.5 percent of theory). bp=124 to 130° C./6μ.

The product can also be obtained by recrystallization from ether and dryice bath cooling.

EXAMPLE 2 Preparation of p-Formylphenyl Vinylbenzyl Ether

By employing the method and two-thirds of the quantities of Example 1,substituting p-hydroxybenzaldehyde for salicylaldehyde, and purifyingthe reaction product by recrystallization from isopropanol andt-butanol, 15.8 g (6.6 percent of theory) of p-formylphenyl vinylbenzylether were obtained. mp=77° to 80° C.

EXAMPLE 3 Preparation of m-Formylphenyl Vinylbenzyl Ether

A mixture of 30.0 g (0.245 mol) of m-hydroxybenzaldehyde, 38.4 (0.251mol) of vinylbenzyl chloride, 17.6 g of 85 percent potassium hydroxide,0.4 g of m-dinitrobenzene and 570 ml of 3A alcohol was heated at refluxfor 18.25 hours. The mixture was cooled, filtered and the filtrate wasconcentrated. The residue was treated with ether and filtered. Thefiltrate was washed three times with 5 percent sodium hydroxide and twotimes with water. The organic phase was dried over sodium sulfate andconcentrated to an oil. The oil distilled in the presence ofm-dinitrobenzene inhibitor. The yield of m-formylphenyl vinylbenzylether was 26.0 g (44.50percent of theory). bp=104°-119° C./3.0-10.0μ.

Preparations 1 through 4 illustrate the preparation of homopolymers fromsome aldehyde-containing polymerizable monomers.

PREPARATION 1 Solution Polymerization of o-Formylphenyl VinylbenzylEther

A solution of 5.0 g of o-formylphenyl vinylbenzyl ether and 20 ml ofp-dioxane was purged with nitrogen.

2,2'-Azobis(2-methylpropionitrile) (0.025 g) was added, and the solutionwas heated in a 60° C. bath with nitrogen bubbling for 21 hours. Theresultant solution was poured into diethyl ether to precipitate polymer,which was subsequently washed with ether and dried in vacuo. The yieldof polymer was 2.9 g (58.0 percent of theory). The inherent viscosity ofthe polymer was 0.22 ((as measured at 25 percent in a 1:1 (weight)solution of phenol and chlorobenzene)), and the Tg was 52° C. Thepolymer was soluble in tetrahydrofuran.

PREPARATION 2 Solution Polymerization of p-Formylphenyl VinylbenzylEther

p-Formylphenyl vinylbenzyl ether was polymerized by a method like thatof Preparation 1. The resulting polymer had an inherent viscosity of0.19. The polymer was soluble in tetrahydrofuran. The yield was 30.0percent of theory.

PREPARATION 3 Solution Polymerization of m-Formylphenyl VinylbenzylEther

A solution of 5.0 g of m-formylphenyl vinylbenzyl ether and 5 ml ofp-dioxane was purged with nitrogen. 2,2'-Azobis(2-methylpropionitrile)(0.0125 g) was added, and the solution was heated in a 60° C. bath withnitrogen bubbling for 16 hours. The solution was then poured intodiethyl ether to precipitate the resulting polymer which was collectedand dried in vacuo. The yield of polymer was 1.0 g (20.0 percent oftheory). The polymer had an inherent viscosity of 0.26, a glasstransition temperature of -4° C. and was soluble in tetrahydrofuran.

PREPARATION 4 Emulsion Polymerization of p-Formylphenyl VinylbenzylEther

An emulsion of 23.0 g (0.096 moles) of p-formylphenyl vinylbenzyl ether,1.15 g of Duponol ME surfactant (Tradename of E. I. duPont de Nemours)and 69.0 g of distilled water was purged with N₂ and, thereafter, 0.1 gof K₂ S₂ O₈ and 0.033 g NaHSO₃ were added while stirring. The emulsionwas heated in a 60° C. bath for 2.5 hours under N₂ with continuousstirring. It was filtered through glass wool to remove an orange-brownprecipitate, giving 85.2 g of latex. A sample of this latex was frozen,thawed and filtered to collect the resulting polymer. The polymer waswashed with water and dried in a vacuum oven. The solids concentrationwas determined to be 26.0 percent, which corresponded to 85.5 percentconversion.

Examples 4 through 11 illustrate the preparation of some of thecopolymers of the present invention.

EXAMPLE 4 Solution Polymerization of o-Formylphenyl Vinylbenzyl Etherand N1-Butyl-N-4-Methacryloylsulfanilamide

A mixture of 4.76 g (0.02 mol) of o-formylphenyl vinylbenzyl ether, 5.93g (0.02 mol) of N-1-butyl-N-4-methacryloylsulfanilamide and 40 ml ofp-dioxane was purged with nitrogen. 2,2'-Azobis(2-methylpropionitrile)(0.05 g) was added, and the mixture was heated in a 60° C. bath withnitrogen bubbling. A solution resulted at 60° C. After approximately 21hours, the solution was poured into diethyl ether to precipitate theresulting polymer. The polymer was collected, washed with ether anddried in vacuo. The polymer had an inherent viscosity of 0.52, a Tg of94° C. and was soluble in acetone. The yield was 8.8 g (82.3 percent oftheory).

EXAMPLE 5 Solution Copolymerization of o-Formylphenyl Vinylbenzyl Etherand Methyl Methacrylate

A mixture of 4.76 g (0.02 mol) of o-formylphenyl vinylbenzyl ether, 2.0g (0.02 mol) of methyl methacrylate and 25 ml of p-dioxane was purgedwith nitrogen. 2,2'-Azobis(2-methylpropionitrile) (0.034 g) was added,and the resulting solution was heated in a 60° C. bath with nitrogenbubbling for 18 hours. The solution was then poured into diethyl etherand the resulting precipitated polymer was isolated and dried. A yieldof 3.2 g (47.4 percent of theory) was obtained.

The polymer had an inherent viscosity of 0.40 and a Tg of 60° C. It wassoluble in tetrahydrofuran and dichloromethane.

Other copolymers of o-formylphenyl vinylbenzyl ether and variouscomonomers were prepared in similar fashion to the copolymers ofExamples 4 and 5. These copolymers are listed along with severalproperties in Table I below.

                  TABLE I                                                         ______________________________________                                                            Polymer Properties                                        Ref-                                 Soluble                                  erence                                                                              Comonomer        I.V.   Tg(°C.)                                                                       In                                       ______________________________________                                        Ex. 6 N-(p-tolylsulfonyl)-                                                                           0.71   63     acetone                                        carbamic acid(male-                                                           inimido)methyl ester                                                    Ex. 7 methyl vinyl ketone                                                                            0.62   58     tetrahy-                                                                      drofuran                                 Ex. 8 N-butyl-4-methacryl-                                                                           0.59   61     acetone                                        oyloxybenzenesulfonamide                                                Ex. 9 N-1-ethyl-N-4-methacryl-                                                                       0.26   56     acetone                                        oylsulfanilamide                                                        ______________________________________                                    

EXAMPLE 10 Terpolymerization of o-Formylphenyl Vinylbenzyl Ether,N-(2,6-Dihydroxyphenyl)acrylamide, and2-(Methacryloyloxy)ethyltrimethylammonium Methosulfate

A solution of 1.19 g (0.005 mole) of o-formylphenyl vinylbenzyl ether,3.58 g (0.020 mole) of N-(2,6-dihydroxyphenyl)acrylamide, 7.08 g (0.025mole) of 2-(methacryloyloxy)ethyltrimethylammonium methosulfate and 107ml of N,N-dimethylformamide was purged with nitrogen.2,2'-Azobis(2-methylpropionitrile) (0.118 g) was added, and the solutionwas heated in a 60° C. bath with nitrogen bubbling for approximately 21hours. The solution was poured into acetone to precipitate polymer,which was collected and dried at room temperature, in vacuo. The yieldof polymer was 12.1 g (100 percent conversion plus retained solvent).The inherent viscosity was determined to be 2.52 (in water), and theglass transition temperature on second heating was 103° C.

EXAMPLE 11 Copolymerization of o-Formylphenyl Vinylbenzyl Ether and2-(Methacryloyloxy)ethyltrimethylammonium Methosulfate

A solution of 8.51 g (0.03 mole) of2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 2.38 g (0.01mole) of o-formylphenyl vinylbenzyl ether, and 98 ml ofN,N-dimethylformamide was purged with nitrogen.2,2'-Azobis(2-methylpropionitrile) (0.054 g) was added, and the solutionwas heated in a 60° C. bath for 19 hours. The solution was poured intoether to precipitate polymer, which was rinsed again with ether andpartially dried. The polymer was dissolved in methanol, reprecipitatedinto ether, isolated and dried in vacuo. The yield of polymer was 8.4 g(77.1 percent conversion). The inherent viscosity was determined to be1.09 (in DMF), and the glass transition temperature was found to be 97°C. on third heating.

EXAMPLE 12

This example demonstrates how the polymers of the present invention canbe used in elements from which negative relief images can be made.

In 1.8 g of a 10 percent solution of poly(o-formylphenyl vinylbenzylether) in A.C.S. grade tetrahydrofuran (THF) were dissolved 20 mg of2-isopropoxy-1,4-naphthoquinone, a photoactivator, and 5 mg of2,2'-bipyridine. To this was added a solution of 20 mg [(NH₂ [CH₂ ]₃NH₂)Co]-(CF₃ CO₂)₃ ((tris(trimethylenediamine) cobalt(III)trifluoroacetate)) in 200 mg of 2-methoxyethanol. This dope was coatedwith a 100-micron doctor blade on subbed poly(ethylene terephthalate)support. The dried coating was given an exposure of 3200 erg/cm² at 320nm and heated for 10 seconds, coating side up, on a 90° C. hot block.Exposure was achieved by using a monochromatic spectral sensitometerthat allows the isolation of comparatively narrow bands of the spectrumand a determination of the photographic response to the material to theradiation of the spectral region selected. The output radiation from anair-cooled, water-filtered, 1000-watt, high-pressure Xenon lamp waspassed through quartz optics and was focused upon the entrance slits ofa Bausch and Lomb 1/4-meter, high-intensity monochromator. The output ofthe monochromator was filtered with broad bandpass filters to removehigher order radiation, passed through a Uniblitz electronic shutter andfinally impinged upon the photographic material. As the irradiation areaof the material was small, the exposures corresponding to the differentsteps of a sensitometric step tablet could not be made at the same time,but were made in succession with the exposure, being time-modulated toproduce the range of exposures required. To compute the irradiance ofthe sensitometer, it was necessary first to determine wavelength regionsat which the exposure was to be made. The irradiance per unit time wasmeasured at a given exposure distance with a Hewlett-Packard Flux Meter,Model 8330A, and a Hewlett-Packard Flux Detector, Model 8334A. The 320nm exposure of this example was conducted at a wavelength very close tothe λ_(max) of the 2-isopropoxy-1,4-naphthoquinone (λ_(max) =327 nm) foran amount of time required to give an exposure of 3200 ergs per squarecentimeter.

The coating was then immersed in an agitated mixture of 2:1, by volume,THF:p-dioxane. The unexposed areas were removed, leaving a reliefnegative image.

Although the present invention has been described in considerable detailwith reference to certain preferred embodiments thereof, it will beunderstood that variations and modifications can be effected withoutdeparting from the spirit and scope of the invention.

What is claimed is:
 1. An uncrosslinked polymer formed by free radicalpolymerization of:(a) about 1 to about 99 mole percent of one or moremonomers having the formula (I): ##STR8## wherein: R, R¹, R² and R³ areindependently hydrogen or alkyl containing from 1 to 4 carbon atoms;R⁴is arylene containing 6 to 18 carbon atoms; m is an integer from 1 to 4;and n is an integer from 0 to 4; and (b) about 1 to about 99 molepercent of one or more additional ethylenically unsaturatedpolymerizable monomers having substituents which are susceptible todegradation by a base.
 2. The polymer of claim 1 wherein R, R¹, R² andR³ are hydrogen.
 3. The polymer of claim 2 wherein m is 1 and n is
 0. 4.The polymer of claim 3 wherein R⁴ is phenylene.
 5. The polymer of claim1 wherein the one or more additional ethylenically unsaturatedpolymerizable monomers are selected from the group consisting of vinylesters, vinyl amides, vinyl halides, vinyl nitriles, vinyl ketones,unsaturated acids or functional derivatives thereof, andsulfonamido-containing monomers.
 6. The polymer of claim 5 wherein theone or more additional ethylenically unsaturated polymerizable monomersare sulfonamido-containing monomers.
 7. The polymer of claim 6 whereinthe additional ethylenically unsaturated polymerizable monomer isN-butyl-4-methacryloyloxybenzenesulfonamide.
 8. The polymer of claim 1having an inherent viscosity within the range of from about 0.1 to about2.0.
 9. An uncrosslinked polymer formed by free radical polymerizationof:(a) about 1 to about 99 mole percent of o-formylphenyl vinylbenzylether; and (b) about 1 to about 99 mole percent ofN-butyl-4-methacryloyloxybenzenesulfonamide.
 10. A method of making anuncrosslinked polymer formed by free radical polymerization of:(a) about1 to 100 mole percent of one or more monomers having the formula (I):##STR9## wherein: R, R¹, R² and R³ are independently hydrogen or alkylcontaining from 1 to 4 carbon atoms;R⁴ is arylene containing 6 to 18carbon atoms; m is an integer from 1 to 4; and n is an integer from 0 to4; and (b) from about 0 to about 99 mole percent of one or moreadditional ethylenically unsaturated polymerizable monomers, the methodcomprising:(1) reacting, in the presence of an acid acceptor, a compoundhaving the formula: ##STR10## with a compound having the formula HO-R⁴--CHR³)_(n) CHO wherein X is halide and R, R¹, R², R³, m and n are asdefined above for formula (I); and (2) homopolymerizing orcopolymerizing the resulting aldehyde-containing monomer with the one ormore additional ethylenically unsaturated polymerizable monomers. 11.The method of claim 10 wherein R, R¹, R² and R³ are hydrogen.
 12. Themethod of claim 11 wherein m is 1 and n is
 0. 13. The method of claim 12wherein R⁴ is phenylene.
 14. The method of claim 10 wherein step (1) iscarried out at a temperature of from about 70° to about 90° C. at aboutatmospheric pressure.
 15. The method of claim 10 wherein the startingmolar ratio in step (1) of the compound having the formula: ##STR11## tothe compound having the formula HO-R⁴ --CHR³)_(n) CHO is from about1:0.09 to about 1:1.1.
 16. The method of claim 10 wherein the acidacceptor is an hydroxide.
 17. The method of claim 10 wherein the one ormore additional ethylenically unsaturated polymerizable monomers havesubstituents which are susceptible to degradation by a base.
 18. Themethod of claim 17 wherein the one or more additional ethylenicallyunsaturated polymerizable monomers are selected from the groupconsisting of vinyl esters, vinyl amides, vinyl halides, vinyl nitriles,vinyl ketones, unsaturated acids or functional derivatives thereof, andsulfonamido-containing monomers.
 19. The method of claim 18 wherein theone or more additional ethylenically unsaturated polymerizable monomersare sulfonamido-containing monomers.
 20. The method of claim 19 whereinthe additional ethylenically unsaturated polymerizable monomer isN-butyl-4-methacryloyloxybenzenesulfonamide.
 21. The method of claim 10wherein the polymer produced has an inherent viscosity within the rangeof from about 0.1 to about 2.0.
 22. The method of claim 10 wherein step(2) is carried out in an organic solvent.